2/25/2024

MATERIAL SCIENCE &

ENGINEERING
LIBYAN ACADEMY FOR POSTGRADUATE STUDIES

SCHOOL OF APPLIED SCIENCES AND ENGINEERING

DEPARTMENT OF MEDICAL ENGINEERING

Diffusion

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Diffusion

Materials of all types are often heat-treated to improve their

properties. The phenomena that occur during a heat treatment
almost always involve atomic diffusion.
Heat treating temperatures and times and/or cooling rates can often
be predicted by using the mathematics of diffusion and appropriate
diffusion constants.

Diffusion

Diffusion is the migration of atoms from a region

of high concentration to a region of low
concentration

in metals diffusion can occur by two different

mechanisms: interstitial diffusion and substitutional
diffusion.

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Diffusion
Interstitial diffusion occurs
if a solute atom is
sufficiently small and moves
to a position between larger
solvent atoms in an energy-
favorable configuration.
Atoms move from an
interstitial position to another
interstitial site nearby.

Diffusion
Substitutional diffusion occurs only if a vacancy is present. A
vacancy is a “missing atom” in the lattice. If a vacancy is
present, one of the adjacent atoms can move into the vacancy,
creating a vacancy on the site that the atom has just left.

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Substitutional Diffusion

 Example: If atom ‘A’

has sufficient activation
energy, it moves into the
vacancy self diffusion.

Activation Activation Activation

Energy of = Energy to + Energy to
Self diffusion form a move a
Vacancy vacancy

 As the melting point increases, activation energy also increases

Diffusion
Vacancy or Substitutional Diffusion mechanism

 Atoms diffuse in solids if

 Vacancies or other crystal defects are present
 There is enough activation energy

 Atoms move into the vacancies present.

 More vacancies are created at higher temperature.
 Diffusion rate is higher at high temperatures.
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Diffusion
Steady State Diffusion

Concentration
C1

Of diffusing
C2
 There is no change in

atoms
concentration of solute
atoms at different planes in a
system, over a period of
Net flow
time. Unit of atoms
Diffusing
atoms Area Per unit
 No chemical reaction area per
occurs. Only net flow of Unit time
=J
atoms. Distance x

Diffusion

STEADY STATE DIFFUSION

The flux or flow of atoms is given by

J = Flux or net flow of atoms.
D = Diffusion coefficient.
dc
J  D dc
= Concentration Gradient.
dx dx
FICK’S LAW

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Diffusion

 Diffusivity depends upon

 Type of diffusion : Whether the diffusion is interstitial or substitutional.
 Temperature: As the temperature increases diffusivity increases.
 Type of crystal structure: BCC crystal has lower APF than FCC and hence
has higher diffusivity.
 Type of crystal imperfection: More open structures (grain boundaries)
increases diffusion.
 The concentration of diffusing species: Higher concentrations of diffusing
solute atoms will affect diffusivity.

Diffusion

The Amount or Rate of Diffusion

moles (or mass) diffusing mol kg

J  Flux   or
surface area  time cm 2 s m2 s

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Diffusion
Steady-State Diffusion Rate of diffusion independent of time
dC
Flux proportional to concentration gradient =
dx

C1 C1

Fick’s first law of diffusion

C2 C2

dC
x1
x
x2 J  D
dx
dC C C2  C1
if linear   D  diffusion coefficient
dx x x2  x1

Example:
Chemical Protective Clothing
Methylene chloride is a common ingredient of paint removers. Besides being
an irritant, it also may be absorbed through skin. When using this paint
remover, protective gloves should be worn. If butyl rubber gloves (0.04 cm
thick) are used, what is the diffusive flux of methylene chloride through the
glove?
Data:
Diffusion coefficient in butyl rubber: D = 110x10-8 cm2/s

C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
face concentrations

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Example (Continue)
Solution – assuming linear concentration gradient dC C  C1
J -D  D 2
dx x2  x1
Data: D = 110 x 10-8 cm2/s
C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
x2 – x1 = 0.04 cm

Since the diffusion coefficient is the movement of a

substance through a unit of area in one second thus
the units of the diffusion coefficient or diffusivity unit
are square meters per second (m𝟐 /s)

(0.02 g/cm3  0.44 g/cm3 ) g

J   (110 x 10-8 cm2 /s)  1.16 x 10-5
(0.04 cm) cm2s

Diffusion and Temperature

• Diffusion coefficient increases with increasing T.

 Qd 
D  D0 exp   
 RT 
D = diffusion coefficient [m2/s]
Do = pre-exponential [m2/s]
Qd = activation energy [J/mol or eV/atom]
 Qd  R = gas constant [8.314 J/mol-K]
 
D  D0 e  RT  T = absolute temperature [K]

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Diffusion and Temperature

• Diffusion coefficient increases with increasing T.
 Qd 
 
D  D0 e  RT 

Example:
At 300ºC the diffusion coefficient and activation energy
for Cu in Si are :
D (300ºC) = 7.8 x 10-11 m2/s , Qd = 41.5 kJ/mol
What is the diffusion coefficient at 350ºC?

 Qd 
 
D  D0 e  RT 

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Example (Continue)
 Qd 
 
D  D0 e  RT 

  Qd 
     Qd    Q 
ln D  ln D0 e  R T  
 ln D  ln D0  ln e  R T   ln D  ln D0    d 




   RT 
 
Qd Qd  1 
ln D  ln D0  ln D  ln D0   
RT R  T

 1
Qd 
lnD2  lnD0    
 T2 
R   1 1
  lnD2  lnD1  ln
D2 Q
 d   
Q 1 
lnD1  lnD0  d   
D1 R  T2 T1 
R  T1  

Example (Continue)

D2 Q 1 1  Q  1 1 
ln  d    D2  D1 exp d   
D1 R  T2 T1   R  T2 T1 

T1 = 273 + 300 = 573K T2 = 273 + 350 = 623K

 J 
  41.5  10 3
D2  (7.8 x 10 11 m 2 /s) exp  mol  1  1 
 
 8.314 J  623 K 573 K 
 mol - K 
D2 = 156.9 38x 10-12 m2/s D2 = 15.7 x 10-11 m2/s

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Non-steady State Diffusion

 The concentration of diffusing species is a function of both time and

position C = C(x,t)
 In this case Fick’s Second Law is used

C  2C
Fick’s Second Law D 2
t x

Non-steady State Diffusion

 Copper diffuses into a bar of aluminum.

Surface conc.,
C s of Cu atoms bar
pre-existing concentration, Co of copper atoms

Cs
Boundary Conditions B.Cs.
at t = 0, C = Co for 0  x  
at t > 0, C = CS
for x = 0 (constant surface concentration)
C = Co for x = 

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Non-steady State Diffusion

Solution of the equation
C  2C C x , t   Co  x 
D 2  1  erf  
t x Cs  Co  2 Dt 

Cs = Surface concentration of element in gas diffusing CS

into the surface. Time = t2
C0 = Initial uniform concentration of element in solid. Cx Time= t1
Cx = Concentration of element at distance x from surface at
C(x,t) Time = t0
time t2.
x = distance from surface
Co
D = diffusivity of solute
x Distance x
t = time.

Non-steady State Diffusion

Solution of the equation
C  2C C x , t   Co  x 
D 2  1  erf  
t x Cs  Co  2 Dt 

C(x,t) = Concentration at point x at time t CS

erf (z) = error function

C(x,t)
2 z y 2
 0
 e dy Co

erf(z) are tabulated values

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Example:

An FCC iron-carbon alloy initially containing 0.20 wt% C is carburized at an elevated

temperature and in an atmosphere that gives a surface carbon concentration constant at 1.0
wt%. If after 49.5 h the concentration of carbon is 0.35 wt% at a position 4.0 mm below the
surface, determine the temperature at which the treatment was carried out.

CS
 Co = 0.20 wt% Time = t2
 Cs = 1.0 wt% Cx Time= t1

 t = 49.5 h, Cx,t = 0.35 wt% = C(x,t), x = 4 x 10- C(x,t) Time = t0

3m
Co

C( x , t )  Co  x 
 1  erf   x Distance x
Cs  Co  2 Dt 

Example (continue): C( x , t )  Co  x 
 1  erf  
Cs  Co  2 Dt 

 Co = 0.20 wt%
 Cs = 1.0 wt%
 C (x,t) = 0.35 wt% t = 49.5 h, x = 4 x 10-3 m

 x 
C( x, t )  Co 0.35  0.20
0.1875  1  erf    1  erf ( z )
 x 
  1  erf    1  erf ( z )  2 Dt 
Cs  Co 1.0  0.20  2 Dt 
erf ( z )  1  0.1875
erf ( z )  0.8125

erf(z) = 0.8125

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Example (continue):
erf(z) = 0.8125

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Example (continue):
from the table, we can determine the value of z for which the error
function is 0.8125.
by using the linear interpolation:  x 
0.1875  1  erf    1  erf ( z )
 2 Dt 
z erf(z) erf ( z )  1  0.1875
0.90 0.7970 erf ( z )  0.8125
z 0.8125
0.95 0.8209
Now solve for D x x2
z  0.90 0.8125  0.7970 z D
 2 Dt 4 z 2t
0.95  0.90 0.8209  0.7970

z  0.93
 x2  3 2
D     ( 4 x 10 m) 1h
 2.6 x 1011 m2 /s
 4z 2t  ( 4)(0.93)2 ( 49.5 h) 3600 s
 

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Example (continue):

To solve for the temperature at which D has above value

Qd  1  ln D Q 1 Qd  1 
ln D  ln D0     d   ln D  ln D0    
R  T ln D0 R  T R  T

Qd  1 
 ln D0  ln D  
Qd  1 
   ln D0  ln D     
R  T R  T

ln D0  ln D   Qd  1 
Qd
ln D0  ln D   R  T  Qd T
R  T R(lnDo  lnD)

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from Tables, for diffusion of C in FCC Fe

Do = 2.3 x 10-5 m2/s Qd = 148 kJ/mol
Qd
T
R(lnDo  lnD)

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Example (continue):

from Tables, for diffusion of C in FCC Fe

Do = 2.3 x 10-5 m2/s Qd = 148 kJ/mol Qd
T
R(lnDo  lnD)

J
148  10 3
T mol
 J   5 m
2
11 m 
2
 8.314   ln 2.3x10  ln 2.6x10 
 mol - K   s s 

T = 1300 K = 1027°C
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